期刊
PHYSICAL REVIEW E
卷 105, 期 5, 页码 -出版社
AMER PHYSICAL SOC
DOI: 10.1103/PhysRevE.105.054502
关键词
-
资金
- National Science Centre [DEC2018/29/B/ST3/00889]
- National Science Foundation [CHE-1753282]
This paper compares the thermodynamics, ionic dynamics, and mechanical properties of pendant and backbone polymerized ionic liquids (PILs). The results show that pendant PILs have lower energy barrier for ion hopping and stronger sensitivity to pressure. A free-volume based model is proposed to explain the ion dynamics of these PILs under high-pressure conditions.
Polymerized ionic liquids (PILs) are typically single-ion conductors, where one kind of ionic species is either placed as the pendant group to the chain (pendant PILs) or directly incorporated into the polymeric backbone (backbone PILs). This paper compares the thermodynamics, ionic dynamics, and mechanical properties of pendant and backbone PILs. The results indicate that near the glass transition, the energy barrier for ion hopping is much lower for pendant PIL while the backbone PIL shows a much stronger sensitivity to pressure. At the same time, a free-volume based model was proposed here to understand the ion dynamics of both studied PILs at high-pressure conditions. The determined critical volume, quantifying the minimal volume required for ion hopping, of the pendant PIL is significantly reduced compared to the backbone PIL, which is most likely the reason for the enhanced ionic conductivity of the pendant PIL near the glass transition. We found that the proposed model is equivalent to the commonly used pressure counterpart of the Vogel-Fulcher-Tammann equation.
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